74-88-4

The gas-phase ion-molecule association reaction CH3I+ + CH3I ? [CH3-I-I-CH3]+ in various bath gases was studied at 503 K. The iodine-iodine bond in the association product is an example of a two-center three-electron (2c-3e) or a 2σ/1σ* bond. The bond energy was estimated from ΔG° of reaction, which was in turn determined from equilibrium experiments. Assuming a value for ΔS° of reaction of -20 to -25 cal/(mol K), a bond strength of 23-26 kcal/mol is estimated. This is the first experimental gas-phase binding energy estimate for a 2c-3e bond in an organic molecule involving an iodine-iodine interaction and one of only a few experimental studies of well-characterized gas-phase 2c-3e bonding interactions between heteroatoms in organic molecules. A study of the ion-molecule reactions occurring at low ionizing energies leading to (CH3)2I+, [C2H3I2]+, and [CH3-I-I-CH3]+ is discussed.

Three different [Ir(LL′)(cod)] complexes (LL′?=?N-aryl-N-nitrosohydroxylaminato) (cupf), trifluoroacetylacetonato (tfaa), and (methyl 2-(methylamino)-1-cyclopentene-1-dithiocarboxylato-κN,κS) (macsm)) were synthesized, characterized, and their rates of oxidative addition with methyl iodide were determined. Formation of an isosbestic point during the oxidative addition of methyl iodide with the complexes containing tfaa and cupf as bidentate ligands indicated formation of only one product, while an increase in absorbance maximum observed for macsm confirms that the same reaction between the complex and methyl iodide occurs. Kinetic results for all complexes, except [Ir(tfaa)(cod)], showed simple second-order kinetics with a zero intercept (within experimental error). Rates of oxidative addition for bidentate ligands in acetonitrile showed an increase of an order of magnitude with a change in the type of bidentate ligands. Computational chemistry using density functional theory calculations showed that the oxidative addition reaction proceeds through a “linear” transition state with the methyl iodide unit tilted towards the LL′-bidentate ligand.

-

A monohalomethane-producing enzyme, S-adenosyl-L-methionine-dependent halide ion methyltransferase (EC 2.1.1.-) was purified from the marine microalga Pavlova pinguis by two anion exchange, hydroxyapatite and gel filtration chromatographies. The methyltransferase was a monomeric molecule having a molecular weight of 29,000. The enzyme had an isoelectric point at 5.3, and was optimally active at pH 8.0. The Km, for iodide and SAM were 12 mM and 12 μM, respectively, which were measured using a partially purified enzyme. Various metal ions had no significant effect on methyl iodide production, suggesting that the enzyme does not require metal ions. The enzyme reaction strictly depended on SAM as a methyl donor, and the enzyme catalyzed methylation of the I , Br , and Cl- to corresponding monohalomethanes and of bisulfide to methyl mercaptan.

Radical cations from methyl iodide, CH3I.+, and are shown to be excellent oxidants with a one-electron redox potential presumably >/= +2 V.Absolute rate constants in the order of 1E9 M-1s-1 have been determined for their reactions with various organic sulfides, disulfides thiols, phenothiazines, and inorganic metal and halide ions.A similarly high reactivity has also been found for the hydroxyl radical adduct to methyl iodide, CH3I(OH)..The results are discussed in view of electronic and steric structure of these oxidizing radical species and the substrates to be oxidized.

-

The reaction between sulfur dioxide and iodine in methanol is started by traces of water in the solvent. Hydrogen iodide is formed and reacts with methanol to produce more water until all iodine is used up. An addition compound between iodine and hydrogen sulfite was found as an intermediate and characterized by Raman spectroscopy. Elementary sulfur is formed in a second reaction.

Thermal behaviour of heptakis-6-iodo-6-deoxy-beta-cyclodextrin (HIDBCD) under inert and oxidative conditions was investigated by TG/DTG/DTA, FTIR, and using the hyphenate technique TG-FTIR. Due to the fact that thermal behaviour of HIDBCD was not studied before, we set our goal in the investigation of thermal degradation process in a dynamic air atmosphere vs. nitrogen atmosphere at a heating rate of 10 °C min-1, up to 500 °C, respectively, 600 °C. It was found that the degradation process in air occurs in a single step, with a total mass loss of 99.9 %. The results of TG/DTG/DTA-FTIR indicated that the thermal behaviour of this cyclodextrin can be divided into three stages and more information was provided about the reaction sequences and the relevant products of reaction.

-

The kinetics of the reaction of the CH2I and CH3 radicals, R, with HBr have been investigated separately in a heatable tubular reactor coupled to a photoionization mass spectrometer. The CH2I (or CH3) radical was produced homogeneously in the reactor by a pulsed 248 or 351 nm exciplex laser photolysis of CH2I2 (or CH3I). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately over a wide ranges of temperatures and the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student's t values, units in cm3 molecule-1 s-1): k(CH2I + HBr) = (3.8 ± 0.7) × 10-13 exp[+ (1.4 ± 0.6) kJ mol-1/RT] and k(CH3 + HBr) = (2.3 ± 0.5) × 10-12 exp[+ (0.60 ± 0.17) kJ mol-1/RT]. The threshold energies of the reverse reactions, Br + R′H → R′ + HBr (R′ = CH2I, CHI2 or CI3), were calculated by ab initio methods at the MP2(fc)/6-311G(df)//MP2(fc)/6-311G(df) level of theory. These were combined with the experimentally determined activation energies of the forward reactions in a second-law method to determine the enthalpies of the reactions. The enthalpy of formation values at 298 K are (in kJ mol-1): 228.0 ± 2.8 (CH2I), 314.4 ± 3.3 (CHI2) and 424.9 ± 2.8 (CI3). The C-H bond strengths of analogous iodomethanes are (in kJ mol-1): 431.6 ± 2.8 (CH3I), 412.9 ± 3.3 (CH2I2) and 391.9 ± 3.1 (CHI3). The Arrhenius expression of the reverse reactions as determined by the thermodynamic transition state theory. The entropies of activation of the reactions were obtained by ab initio calculations.

Rationale: Stable hydrogen and carbon isotope ratios of methoxy groups (OCH3) of plant organic matter have many potential applications in biogeochemical, atmospheric and food research. So far, most of the analyses of plant methoxy groups by isotope ratio mass spectrometry have employed liquid iodomethane (CH3I) as the reference material to normalise stable isotope measurements of these moieties to isotope–δ scales. However, comparisons of measurements of stable hydrogen and carbon isotopes of plant methoxy groups are still hindered by the lack of suitable reference materials. Methods: We have investigated two methyl sulfate salts (HUBG1 and HUBG2), which exclusively contain carbon and hydrogen from one methoxy group, for their suitability as methoxy reference materials. Firstly, the stable hydrogen and carbon isotope values of the bulk compounds were calibrated against international reference substances by high-temperature conversion- and elemental analyser isotope ratio mass spectrometry (HTC- and EA-IRMS). In a second step these values were compared with values obtained by measurements using gas chromatography/isotope ratio mass spectrometry (GC/IRMS) where prior to analysis the methoxy groups were converted into gaseous iodomethane. Results: The 2H- and 13C isotopic abundances of HUBG1 measured by HTC- and EA-IRMS and expressed as δ-values on the usual international scales are ?144.5 ± 1.2 mUr (n = 30) and ?50.31 ± 0.16 mUr (n = 14), respectively. For HUBG2 we obtained ?102.0 ± 1.3 mUr (n = 32) and +1.60 ± 0.12 mUr (n = 16). Furthermore, the values obtained by GC/IRMS were in good agreement with the HTC- and EA-IRMS values. Conclusions: We suggest that both methyl sulfates are suitable reference materials for normalisation of isotope measurements of carbon of plant methoxy groups to isotope–δ scales and for inter-laboratory calibration. For stable hydrogen isotope measurements, we suggest that in addition to HUBG1 and HUBG2 additional reference materials are required to cover the full range of plant methoxy groups reported so far.

A double-charge-transfer spectroscopy study has provided evidence for the existence of four low-lying electronic states of the CH3I2+ ion, the double-ionization energies to which are 27.0 +/- 0.3, 29.6 +/- 0.3, 31.3 +/- 0.5 and 36.5 +/- 0.5 eV.Three of these energies agree, within experimental error, with those determined previously in a dissociative double photoionization study of CH3I.The present investigation reveals for the first time the state at 29.6 eV.The value of the double-ionization energy to the ground triplet state, calculated in the present investigation using the single-determinant Hartree-Fock approximation to the many-electron wavefunction with corrections of second-order Moeller-Plesset perturbation theory for correlation effects, is 25.80 eV, somewhat lower than the measured value of 27.0 eV.

Diiodosilane (DIS), which has never been used previously in organic synthesis, has been shown to exhibit properties and reactivities that are complementary to those of iodotrimethylsilane.This new reagent was used to cleave and deoxygenate ethers and alcohols with high selectivity for secondary oxygen functions.Synthesis of DIS is easily and rapidly carried out by reacting phenylsilane with iodine.

Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is

The synthesis of guanidinium lead iodide, C(NH2)3PbI3 (GUAPbI3), was conducted by slow evaporation of the mixture obtained by dissolving PbI2 and C(NH2)3I in acetonitrile. When the evaporation is done at 40 oC, a yellow needle-like crystals are being formed. The sample was characterized by elemental analysis, density measurements, scanning electron microscopy, thermal analyses, high-temperature X-ray powder diffraction and infrared spectroscopy measurements. The elemental analysis of the obtained crystals confirmed the proposed stoichiometry. The performed thermal analyses showed an endothermic peak associated with structural transition around 160 oC. On the other hand, the endothermic temperature effects above 300 oC are accompanied with mass loss and were interpreted as compound degradation. The crystal structure of high temperature polymorph between 160 oC and 300 oC was determined using high-temperature powder diffraction data measurements at 280 oC using simulated annealing technique in order to obtain initial structural model. The structure was refined using the Rietveld method. At temperatures higher than 160 oC, C(NH2)3PbI3 crystallizes in hexagonal space group P63mc with unit cell parameter a increasing from 9.269 ? to 9.337 ? between 160 oC and 300 oC and c parameter increasing from 15.211 ? to 15.287 ? in the same temperature range. The structure consists of PbI6 octahedra couples sharing a common face, linked with corners. Guanidinium cations are situated in the channels between Pb2I9 couples in a manner that the plane of the molecule is perpendicular to the c-axis.

We show how to improve the yield of MeX from CH4 activation catalysts from 12% to 90% through the use of capping arene ligands. Four (FP)RhIII(Me)(TFA)2 {FP = capping arene ligands, including 8,8′-(1,2-phenylene)diquinoline (6-FP), 8,8′-(1,2-naphthalene)diquinoline (6-NPFP), 1,2-bis(N-7-azaindolyl)benzene (5-FP), and 1,2-bis(N-7-azaindolyl)naphthalene (5-NPFP)} complexes. These complexes and (dpe)RhIII(Me)(TFA)2 (dpe = 1,2-di-2-pyridylethane) were synthesized and tested for their performance in reductive elimination of MeX (X = TFA or halide). The FP ligands were used with the goal of blocking a coordination site to destabilize the RhIII complexes and facilitate MeX reductive elimination. On the basis of single-crystal X-ray diffraction studies, the 6-FP and 6-NPFP ligated Rh complexes have Rh-arene distances shorter than those of the 5-FP and 5-NPFP Rh complexes; thus, it is expected that the Rh-arene interactions are weaker for the 5-FP complexes than for the 6-FP complexes. Consistent with our hypothesis, the 5-FP and 5-NPFP RhIII complexes demonstrate improved performance (from 12% to ～60% yield) in the reductive elimination of MeX. The reductive elimination of MeX from (FP)RhIII(Me)(TFA)2 can be further improved by the use of chemical oxidants. For example, the addition of 2 equiv of AgOTf leads to 87(2)% yield of MeTFA and can be achieved in CD3CN at 90 °C using (5-FP)Rh(Me)(TFA)2.

We report a dual-tasked methylation that is based on cooperative palladium/norbornene catalysis. Readily available (hetero)aryl halides (39 iodides and 4 bromides) and inexpensive MeOTs or trimethylphosphate are utilized as the substrates and methylating reagent, respectively. Six types of "ipso" terminations can modularly couple with this "ortho" C-H methylation to constitute a versatile methylation toolbox for preparing diversified methylated arenes. This toolbox features inexpensive methyl sources, excellent functional-group tolerance, simple reaction procedures, and scalability. Importantly, it can be uneventfully extended to isotope-labeled methylation by switching to the corresponding reagents CD3OTs or 13CH3OTs. Moreover, this toolbox can be applied to late-stage modification of biorelevant substrates with complete stereoretention. We believe these salient and practical features of our dual-tasked methylation toolbox will be welcomed by academic and industrial researchers.

In this paper, we report the iodine mediated in situ generation of R-Se-I and further its application towards the construction of pyrano[4,3-b]quinolin-1-one derivatives. The structural elaboration of 1-chloro-8-methyl-3-phenylbenzo[b][1,6]naphthyridine 6 was successfully achieved by Sonogashira, Suzuki coupling and dehalogenation reactions. Finally, the synthesized compounds 4a, 5a, 5b, 6, and 7a-7c were studied for photophysical properties including UV-absorption, fluorescence, and quantum yield studies. The synthesized pyranoquinoline derivatives showed λmax, Fmax and Φf values in the range of 391-447 nm, 436-486 nm and 0.004-0.301, respectively in chloroform solvent.

A methyl group on an arene, despite its small size, can have a profound influence on biologically active molecules. Typical methods to form a methylarene involve strong nucleophiles or strong and often toxic electrophiles. We report a strategy for a new, highly efficient, copper and iodide co-catalyzed methylation of aryl- and heteroarylboronic esters with the mild, nontoxic reagent trimethylphosphate, which has not been used previously in coupling reactions. We show that it reacts in all cases tested in yields that are higher than those of analogous copper-catalyzed reactions of MeOTs or MeI. The combination of C-H borylation and this methylation with trimethylphosphate provides a new approach to the functionalization of inert C-H bonds and is illustrated by late-stage methylation of four medicinally active compounds. In addition, reaction on a 200 mmol scale demonstrates reliability of this method. Mechanistic studies show that the reaction occurs by a slow release of methyl iodide by reaction of PO(OMe)3 with iodide catalyst, rather than the typical direct oxidative addition to a metal center. The low concentration of the reactive electrophile enables selective reaction with an arylcopper intermediate, rather than nucleophilic groups on the arylboronate, and binding of tert-butoxide to the boronate inhibits reaction of the electrophile with the tert-butoxide activator to form methyl ether.

Hybrid lead halide perovskites have emerged as promising active materials for photovoltaic cells. Although superb efficiencies have been achieved, it is widely recognized that long-term stability is a key challenge intimately determining the future development of perovskite-based photovoltaic technology. Herein, we present reversible and irreversible photodecomposition reactions of methylammonium lead iodide (MAPbI3). Simulated sunlight irradiation and temperature (40-80 °C) corresponding to solar cell working conditions lead to three degradation pathways: (1) CH3NH2 + HI (identified as the reversible path), (2) NH3 + CH3I (the irreversible or detrimental path), and (3) a reversible Pb(0) + I2(g) photodecomposition reaction. If only the reversible reactions (1) and (3) take place and reaction (2) can be avoided, encapsulated MAPbI3 can be regenerated during the off-illumination timeframe. Therefore, to further improve operational stability in hybrid perovskite solar cells, detailed understanding of how to mitigate photodegradation and thermal degradation processes is necessary. First, encapsulation of the device is necessary not only to avoid contact of the perovskite with ambient air, but also to prevent leakage of volatile products released from the perovskite. Second, careful selection of the organic cations in the compositional formula of the perovskite is necessary to avoid irreversible reactions. Third, selective contacts must be as chemically inert as possible toward the volatile released products. Finally, hybrid halide perovskite materials are speculated to undergo a dynamic formation and decomposition process; this can gradually decrease the crystalline grain size of the perovskite with time; therefore, efforts to deposit highly crystalline perovskites with large crystal sizes may fail to increase the long-term stability of photovoltaic devices.

The cyclization of heteroatom-containing alkynes with π acidic metal salts is an attractive method to prepare heterocycles because the starting materials are readily available and the organometallic compounds are useful synthetic intermediates. A new organometallic species in the heterocyclization provides an opportunity to synthesize heterocycles that are difficult to obtain. Herein, we describe a novel cyclic oxymetalation of 2-alkynylbenzoate with indium or gallium salts that proceeds with an unusual regioselectivity to give isocoumarins bearing a carbon-metal bond at the 4-position. This new type of metalated isocoumarin provided 3-unsubstituted isocoumarins that have seldom been investigated despite their important pharmacological properties. Indium and gallium salts showed high performance in the selective 6-endo cyclization of terminal alkynes while boron or other metals such as Al, Au, and Ag caused 5-exo cyclization or decomposition of terminal alkynes, respectively. The metalated isocoumarin and its reaction intermediate were unambiguously identified by X-ray crystallographic analysis. The theoretical calculation of potential energy profiles showed that oxyindation could proceed via 6-endo cyclization under thermodynamic control while previously reported oxyboration would give a 5-membered ring under kinetic control. The investigation of electrostatic potential maps suggested that the differences in the atomic characters of indium, boron and their ligands would contribute to such a regioselective switch. The metalated isocoumarins were applied to organic synthetic reactions. The halogenation of metalated isocoumarins proceeded to afford 4-halogenated isocoumarins bearing various functional groups. The palladium-catalyzed cross coupling of organometallic species with organic halides gave various 4-substituted isocoumarins. A formal total synthesis of oosponol, which exhibits strong antifungal activity, was accomplished.

The invention relates to a synthesis method of a stable isotope-labeled beta receptor agonist type compound. The synthesis method comprises the following steps: (1) by taking stable isotope-labeled methanol as a raw material, reacting with acetone or stable isotope-labeled acetone, and ammonifying to obtain stable isotope-labeled tert-butylamine; and (2) by taking a bromoketone type compound as a precursor of the beta receptor agonist type compound, reacting with stable isotope-labeled tert-butylamine to prepare the stable isotope-labeled beta receptor agonist type compound. Compared with the prior art, the method for preparing the stable isotope-labeled beta receptor agonist, provided by the invention, is simple, safe and reliable, the chemical purity of the product after separation and purification is above 99.0%, the isotopic abundance is above 98.0% atom, and the product can fully meet the requirements of residual detection in the field of food safety.

The coupling reaction of aryl iodides with arenes was found to proceed under mild conditions to give biaryls through a homolytic aromatic substitution mechanism, using potassium tert-butoxide and di-tert-butyl hyponitrite as a stoichiometric promoter and a radical initiator, respectively.

PROBLEM TO BE SOLVED: To provide a high yield manufacturing method of an alkyl iodide compound with iodide salt of a metal or ammonium as a starting material. SOLUTION: Iodide salt of a metal or ammonium is reacted with aliphatic alcohol having 1 to 6 carbon atoms and a Broensted acid in presence of a material having lower oxidation reduction potential than that in monoelectronic oxidation of iodide ions at a reaction temperature of 60 to 120°C. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT

Ni-catalyzed cross-coupling reactions have found important applications in organic synthesis. The fundamental characterization of the key steps in cross-coupling reactions, including C-C bond-forming reductive elimination, represents a significant challenge. Bimolecular pathways were invoked in early proposals, but the experimental evidence was limited. We present the preparation of well-defined (pyridine-pyrrolyl)Ni monomethyl and monophenyl complexes that allow the direct observation of bimolecular reductive elimination to generate ethane and biphenyl, respectively. The sp3-sp3 and sp2-sp2 couplings proceed via two distinct pathways. Oxidants promote the fast formation of Ni(III) from (pyridine-pyrrolyl)Ni-methyl, which dimerizes to afford a bimetallic Ni(III) intermediate. Our data are most consistent with the subsequent methyl coupling from the bimetallic Ni(III) to generate ethane as the rate-determining step. In contrast, the formation of biphenyl is facilitated by the coordination of a bidentate donor ligand.

The methylenation/hydrogenation cascade reaction of aldehydes or ketones through a domino process involving two ensuing steps in a single pot is realized. The compatibility of Matsubara's reagent and Wilkinson's complex give a combination that allows, under dihydrogen, the transformation of a carbonyl function into a methyl group. This new method is suitable to introduce an ethyl motif from aromatic and aliphatic aldehydes with total chemoselectivity and total retention of α-stereochemical purity. The developed procedure is also extended to the introduction of methyl groups from ketones.

A production process of acetic acid according to the present invention inhibits concentration of hydrogen iodide and improves a liquid-liquid separation of an overhead from a distillation column. Acetic acid is produced by distilling a mixture containing hydrogen iodide, water, acetic acid and methyl acetate in a first distillation column (3) to form an overhead and a side cut stream or bottom stream containing acetic acid, cooling and condensing the overhead in a condenser (C3) to form separated upper and lower phases in a decanter (4). According to this process, a zone having a high water concentration is formed in the distillation column above the feed position of the mixture by feeding a mixture having a water concentration of not less than an effective amount to not more than 5% by weight (e.g., 0.5 to 4.5% by weight) and a methyl acetate concentration of 0.5 to 9% by weight (e.g., 0.5 to 8% by weight) as the mixture to the distillation column and distilling the mixture. In the zone having a high water concentration, hydrogen iodide is allowed to react with methyl acetate to produce methyl iodide and acetic acid.

We describe an efficient system for the direct partial oxidation of methane, ethane, and propane using iodate salts with catalytic amounts of chloride in protic solvents. In HTFA (TFA = trifluoroacetate), >20% methane conversion with >85% selectivity for MeTFA have been achieved. The addition of substoichiometric amounts of chloride is essential, and for methane the conversion increases from 20%. The reaction also proceeds in aqueous HTFA as well as acetic acid to afford methyl acetate. 13C labeling experiments showed that less than 2% of methane is overoxidized to 13CO2 at 15% conversion of 13CH4. The system is selective for higher alkanes: 30% ethane conversion with 98% selectivity for EtTFA and 19% propane conversion that is selective for mixtures of the mono- and difunctionalized TFA esters. Studies of methane conversion using a series of iodine-based reagents [I2, ICl, ICl3, I(TFA)3, I2O4, I 2O5, (IO2)2S2O 7, (IO)2SO4] indicated that the chloride enhancement is not limited to iodate.

We reported here the catalytic carbonylation of quaternary ammonium salts under anhydrous condition. Quaternary ammonium salts, a kind of versatile reagents that were widely used in organometallic chemistry, can be carbonylated to tertiary amides by an in situ prepared NaCo(CO)4 catalyst. It was found that the counterions (Cl-, Br-, I-, OTf-) in the quaternary ammonium salts played a significant role in the reaction and tetramethylammonium iodide could give high yield (96%) of N,N-dimethylacetamide (DMAc) with only 0.5 mol% cobalt catalyst. Under optimum conditions, several other quaternary ammonium iodides were also carbonylated to corresponding tertiary amides in moderate to excellent yields. Obviously, these results also give us a special apprehension that Me4NI and other quaternary ammonium salts could be possibly carbonylated to tertiary amides in the carbonylation reaction where they are used as promoters or solvents in most cases. Considering the high activity and moderate to excellent selectivity, this process could be a potential method for the synthesis of certain tertiary amides. Moreover, the cleaving mechanism of CN bonds and the possible catalytic intermediates were discussed in detail.

Disclosed are a reagent for testing the purification capacity of a radioactive gas in a nuclear power plant, preparation method thereof and an iodide filter testing equipment using this reagent. The reagent is prepared by mixing methyl phosphate compound or dimethyl acetal compound, acetonitrile, trimethyl chlorosilane and radioactive iodine sources and carrying out a reaction at a temperature of 20°C-50 °C under an inert gas for 10-40 min. The prepared products except methyl iodide are non-toxic or little toxic to the nuclear grade impregnated activated carbon in the iodide filter.

Methanol carbonylation is the most important process for manufacturing C2 molecules from methanol. The present industrial carbonylation has been proven to be the most successful process on economical grounds. However, there is a request to develop more sustainable and 'green' processes to overcome the inherent drawbacks. Well-designed cross-linked copolymers were prepared and used as support for the simultaneous immobilization of rhodium and iodide species. The resulting catalyst was proven to be highly active in CH3I-free methanol carbonylation and methyl acetate was the main product. Approximately 90% of methanol was converted after a two-hour reaction time at 120 °C under a CO pressure of 3.0 MPa. The immobilization strategy of the active species works efficiently and the present methanol carbonylation catalyst shows good recyclability. After regenerating the catalyst twice over a fifteen-batches test, the catalyst keeps an acceptable activity. The process based on the present catalyst is evidently a promising sustainable methanol carbonylation.

The reaction of 3-alkynyl-4-methoxycoumarins with molecular iodine in chlorinated solvents allows access to 3-iodofurochromones in good to excellent yields as the result of a iodocyclization-demethylation process. Competitive diiodination of the coumarin acetylene moiety could be eliminated by simply performing the reactions in refluxing 1,2-dichloroethane, owing to the thermal instability of the resulting (E)-1,2-diiodoethenylcoumarins. The Royal Society of Chemistry 2011.

Despite the high nucleophilicity of sulfur atoms, thiacalixarenes have been alkylated only on oxygen atoms thus far. Using strong alkylating agents (triflates, trialkyloxonium salts), the substitution of the sulfur bridges has been successfully accomplished. The corresponding sulfonium salts of thiacalix[4]arene are formed regio- and stereoselectively as a completely new type of substitution pattern in thiacalixarene chemistry. These compounds possess interesting conformational behavior and could be used as unusual alkylating agents with uncommon selectivity.

Thermal decomposition of the energetic ionic liquids 1-methyl-4-amino-1,2, 4-triazolium iodide (Me4ATI), 1-methyl-4-amino-1,2,4-triazolium nitrate (Me4ATN), 1-amino-3-methyl-1,2,3-triazolium iodide (Me1ATI), and 1-amino-3-methyl-1,2,3-triazolium nitrate (Me1ATN) was studied by confined rapid thermolysis. Sub-milligram quantities of the compounds were subjected to decomposition under isothermal conditions achieved by initially heating the sample at rates of approximately 2000 K/s. The products formed by decomposition under the afore-mentioned conditions were sampled by rapid scan FTIR spectroscopy and time-of-flight mass spectrometry. Decomposition studies involving the iodide salts were carried out around 270-290.C, whereas the nitrate salts were subjected to 320-340.C. The amino group was found to be involved in the initiation reaction, forming copious quantities of ammonia from the iodide compounds and, N2O and H2 O from the nitrate compounds. The extent of decomposition of the triazole ring was minimal at the considered temperatures.

The reactions of iodo(trimethyl)silane with N,N-dimethylformamide and N,N-dimethylacetamide Me2NCOR (R = H, Me) at a molar ratio of 1: 2 involved mainly cleavage of the N-C(=O) bond with formation of up to 80% of N,N-dimethyltrimethylsilylamine Me3SiNMe2 and the corresponding acyl iodide RCOI. In the reaction with N,N-dimethylformamide, formyl iodide HCOI was detected for the first time by gas chromatography-mass spectrometry. The contribution of Me-N bond cleavage, leading to N-methyl-N-trimethylsilyl derivative Me(Me3Si)NCOR and methyl iodide was considerably smaller. Another by-product was the corresponding N-methyl imide MeN(COR)2 formed by reaction of the initial amide with acyl iodide. The primary intermediate in the reaction of iodo(trimethyl)silane with DMF and DMA is quaternary ammonium salt [Me2(Me3Si)N +COR] I- which decomposes via dissociation of the N-CO and N-Me bonds.

Acyl iodides RCOI (R = Me, Ph) reacted with N,N-dimethylformamide and N,N-dimethylacetamide Me2NC(=O)R' (R' = H, Me) along two concurrent pathways involving transacylation and cleavage of the Me-N bond. The first pathway leads to the formation of acyl group exchange products, and the second, to the corresponding imides R'CON(Me)COR.

Disclosed is an improved carbonylation process for the production of carboxylic acids, carboxylic acid esters, and/or carboxylic acid anhydrides wherein a carbonylation feedstock compound selected from one or more organic oxygenates such as alcohols, ethers, and esters is contacted with carbon monoxide in the presence of a carbonylation catalyst and one or more onium compounds. The carbonylation process differs from known carbonylation processes in that a halide compound, other than the onium salt, such as a hydrogen halide (typically, hydrogen iodide) and/or an alkyl halide (typically, methyl iodide), extraneous or exogenous to the carbonylation process is not fed or supplied to the process. The process can be improved by using a bidentate ligand comprising two functional groups selected from tertiary amines and tertiary phosphines, such as 2,2′-bipyridine and diphosphine derivatives.

This paper investigates the synthetic mechanism of trifluoroiodomethane (CF3I) in the reaction of trifluoromethane and iodine via vapor-phase catalytic reaction. It is suggested that CF2 carbene is the key intermediate and is formed in the pyrolysis process of CHF3 at high temperature. However, in pyrolysis of CHF3 under activated charcoal (AC) existing conditions, no C2F4 was detected. H2 and 2-methyl-2-butene could not trap the CF2 carbene. When treating the remained compounds on the used AC with H2, CH4 is formed on the process. It is proposed that CF2 carbene combines with AC strongly and transfers into CF3 radical on heat. In addition, it is found that the AC is not only the catalyst supporter to form CF3I, but also a co-catalyst to promote the formation of CF2 carbene and CF3 radical.

Aqueous phase reaction of trialkyloxonium tetrafluoroborates, R 3O+BF4- (R=Me, Et) has been tested in the alkylation of simple inorganic anionic substrates such as halogen ions, cyanide, thiocyanate, sulphide an

A simple synthesis of fresh alkyl iodides using alcohols and hydriodic acid (HI) is reported. The alkyl iodides were obtained in quick and easy work-up with good to excellent yields (66-94%) and very high purities (97-99%). Freshly prepared iodomethane and 1-iodobutane were applied to synthesize biologically relevant 3,7-dimethyladenine and 9-butyladenine, which were characterized thoroughly using 1D and 2D NMR, individually.

(Chemical Equation Presented) A four-step mechanism for thermal activation of methylene species on V(100) surfaces to generate propene is identified experimentally (see scheme). Dehydrogenation of methylene to methylidyne and coupling with another methylene group gives a vinyl intermediate, which reacts with a methylene group to form an allyl species, which is finally hydrogenated to propene. This provides evidence for the possible role of vinyl intermediates in Fischer-Tropsch synthesis.

Disclosed is a carbonylation process for the production of carboxylic acids, carboxylic acid esters and/or carboxylic acid anhydrides wherein a carbonylation feedstock compound selected from one or more organic oxygenates such as alcohols, ethers, and esters is contacted with carbon monoxide in the presence of a carbonylation catalyst and one or more onium compounds. The carbonylation process differs from known carbonylation processes in that a halide compound such as a hydrogen halide, typically hydrogen iodide, and/or alkyl halide, typically methyl iodide, extraneous or exogenous to the carbonylation process is not fed or supplied separately to the process.

Reactions of acyl iodides RCOI (R = Me, Ph) with organosilicon compounds involve cleavage of the Si-O-C and Si-O-Si fragments. Acetyl iodide reacts with alkyl(alkoxy)silanes with evolution of heat, and cleavage of the Si-O bond results in the formation of oligo-or polysiloxanes, alkyl iodides, and alkyl acetates. 1,3-Diacetoxytetramethyldisiloxane is formed in the reaction of acetyl iodide with dimethoxy(dimethyl)silane. Acyl iodides readily react with 1-ethoxysilatrane to give 1-acyloxysilatranes as a result of cleavage of the C-O bond. The reaction of acetyl iodide with hexaethyldisiloxane yields triethylsilyl acetate and triethyliodosilane, while in the reaction with octamethyltrisiloxane iodo(trimethyl)silane and dimethyl(trimethylsiloxy)silyl acetate are obtained. Nauka/Interperiodica 2007.

In non-competitive solvents, the tris(3-ureidobenzyl)amines 1a-c form dimeric assemblies in which guests such as CH3CN, CH 3NO2, CH2Cl3, CH3I, CH2BrCl, CH2Br2, CHCl3 and C 6H6 can be encapsulated. Variable temperature 1 and 1H,1H-ROESY NMR spectroscopy, as well as pulsed-gradient spin-echo (PGSE) diffusion measurements were used to in-ivestigate the encapsulation within 1a·1a (1a: tris{3-[N′-(4- butylphenyl)-ureido]benzyl}amine). Kinetic parameters for the encapsulation of CH3NO2, CH2Cl2 and CH3I, both in CDCl3 and in [D8]toluene have been obtained by using magnetisation transfer methods. These data are discussed together with the thermodynamic parameters. The affinity between guest and capsule seems to be dictated mainly by the electronic, size and shape complementarity between cavity and guest. A gating mechanism for guest exchange is proposed.

The yield of triptane from the reaction of methanol with zinc iodide is dramatically increased by addition of phosphorous or hypophosphorous acid, via transfer of hydride from a P-H bond to carbocationic intermediates. The Royal Society of Chemistry.

In this paper, we report the effect of ionic liquids on substitution reactions using a variety of anionic nucleophiles. We have combined new studies of the reactivity of polyatomic anions, acetate, trifuoroacetate, cyanide, and thiocyanide, with our previous studies of the halides in [C4C 1Py][Tf2N], [C4C1py][TfO], and [C4C1im][Tf2N] (where [C4C 1im]+ is 1-butyl-3-methylimidazolium and [C 4C1py]+ is 1-butyl-1-methylpyrrolidinium) and compared their reactivities, k2, to the same reactions in the molecular solvents dichloromethane, dimethylsulfoxide, and methanol. The Kamlet-Taft solvent descriptors (α, β, π*) have been used to analyze the rates of the reactions, which were found to have a strong inverse dependency on the α value of the solvent. This result is attributed to the ability of the solvent to hydrogen bond to the nucleophile, so reducing its reactivity. The Eyring activation parameters (ΔH? and ΔS?), while confirming the reaction mechanism, do not offer obvious correlations with the Kamlet-Taft solvent descriptors.

The catalytic activity of silicon polypodands was evaluated in anion-promoted reactions under solid-liquid phase-transfer catalysis (SL-PTC) conditions and compared with that exhibited by common PTC agents. Results showed that these many-armed ligands are

Integrated processes and systems for producing acetic acid and vinyl acetate are provided. In the processes and systems, a portion of the heat produced during the production of the acetic acid is transferred to the vinyl acetate production and/or purification process and system to facilitate production and/or purification of the vinyl acetate product. The process and systems described herein are useful in conjunction with any of the various known processes for the production of acetic acid and vinyl acetate. The heat of the acetic acid production reaction may be transferred to the vinyl acetate production system by any suitable heat transfer processes and systems. The heat may be provided to the purification section at a variety of locations in the vinyl acetate production and purification systems, depending on the specific configuration of the system to which the processes and systems. The process and systems described herein are useful to provide cost and energy savings in vinyl acetate production processes.

We have continued the study of halide nucleophilicity in ionic liquids, concentrating on the effect of changing the anion ([BF4]-, [PF6] -, [SbF6]-, [OTf]-, and [N(Tf) 2]-) when the cation is [bmim]+ (where bmim = 1-butyl-3-methylimidazolium). It was found that the nucleophilicities of all the halides were lower in all of the ionic liquids than in dichloromethane. Changing the anion affected the order of halide nucleophilicity, e.g., in [bmim][BF4] the order of nucleophilicity was Cl ->Br->I- while in [bmim][N(Tf) 2] the order was Cl---. It was also found that the nucleophilicity of each halide was different in each ionic liquid, with chloride being almost four times as nucleophilic in [bmim][BF4] as in [bmim][SbF6]. Similarly bromide was more than four times as nucleophilic in [bmim][BF4] as in [bmim][PF 6]. The activation parameters ΔG?, ΔH?, and ΔS? have been measured for the reaction of chloride in each of the ionic liquids, plus the reaction of bromide in [bmim][BF4] and [bmim][PF6]. These data were also compared to each other as well as to a similar reaction in dichloromethane (where these parameters have been estimated for both the free ion and the ion-pair). These studies show that the reaction in the ionic liquids has a high activation free energy barrier, due to the solvent-solute interactions within the ionic liquids. These interactions are described and discussed.

A process for the preparation of a quaternary derivative of the morphinan alkaloid, the process comprising contacting a tertiary N-substituted morphinan alkaloid with an alkyl halide in an anhydrous solvent system, wherein the solvent system comprises an aprotic dipolar solvent with the aprotic dipolar solvent constituting at least 25 wt% of the solvent system.

The present invention is directed to labeled compounds, [2H1,13C], [2H2,13C] and [2H3,13C]methyl aryl sulfides wherein the13C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure wherein R1, R2, R3, R4, and R5are each independently, hydrogen, a C1-C4lower alkyl, a halogen, an amino group from the group consisting of NH2, NHR and NRR′ where R and R′ are each a C1-C4lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [2H1,13C], [2H2,13C] and [2H3,13C]methyl aryl sulfides wherein the13C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [2H1,13C]methyl iodide and [2H2,13C]methyl iodide.

The present invention relates to N-alkylated thiazolium salts, to a process for their preparation and also to their use as condensation and dehydrating agents.

This invention relates to certain aryl alkyl acid compounds, compositions, and methods for treating or preventing obesity and related diseases.

Pharmaceutical compositions and compounds are provided. The compounds of the invention have anti-proliferative activity, and may promote apoptosis in cells lacking normal regulation of cell cycle and death. In one embodiment of the invention, formulations of the compounds in combination with a physiologically acceptable carrier are provided. The pharmaceutical formulations are useful in the treatment of hyperproliferative disorders, which disorders include tumor growth, lymphoproliferative diseases, angiogenesis. The compounds of the invention are 1,2,3-thiadiazoles having the structure: and including stereoisomers, solvates, and pharmaceutically acceptable salts thereof, wherein each of R1, R2, R3 and R4 is independently selected from hydrogen, R5, R6, and R7; R5 is selected from alkyl, heteroalkyl, aryl and heteroaryl; R6 is selected from (R5)n-alkylene, (R5)n-heteroalkylene, (R5)n-arylene and (R5)n-heteroarylene; R7 is selected from (R6)n-alkylene, (R6)n-heteroalkylene, (R6)n-arylene, and (R6)n-heteroarylene; and n is selected from 0, 1, 2, 3, 4 and 5, where R1 and R2 may together form a heterocyclic structure including the nitrogen to which they are both attached, and R3 and R4 may together form a heterocyclic structure including the nitrogen to which they are both attached; and each of L1 and L2 is independently selected from -A1-A2-A3- where each of A1, A2, and A3 is independently selected from a direct bond, alkylene, heteroalkylene, arylene and heteroarylene.

The present invention is directed to labeled compounds, [2H1, 13C], [2H2, 13C] and [2H3, 13C]methyl aryl sulfides wherein the 13C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure wherein R1, R2, R3, R4, and R5 are each independently, hydrogen, a C1-C4 lower alkyl, a halogen, an amino group from the group consisting of NH2, NHR and NRR′ where R and R′ are each a C1-C4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [2H1, 13C], [2H2,13C] and [2H3, 13C]methyl aryl sulfides wherein the 13C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [2H1, 13C]methyl iodide and [2H2, 13C]methyl iodide.

Specified phenylalanine derivatives and analogues thereof have an antagonistic activity to α4 integrin. They are used as therapeutic agents for various diseases concerning α4 integrin.

A compound of formula I:

A medicament for preventive and/or therapeutic treatment of a microbial infection which comprises as an active ingredient a compound represented by the following general formula (I): wherein, R1 and R2 represent hydrogen atom, a halogen atom, hydroxyl group or the like, W1 represents —CH═CH—, —CH2O—, —CH2CH2— or the like; R3 represents hydrogen atom, a halogen atom, hydroxyl group or an amino group; R4 represents hydrogen atom, a group of —OZ0-4R5 (Z0-4 represents an alkylene group, a fluorine-substituted alkylene group or a single bond, and R5 represents a cyclic alkyl group, an aryl group or the like); W2 represents a single bond or —C(R8)═C(R9)— (R8 and R9 represent hydrogen atom, a halogen atom, a lower alkyl group or the like, Q represents an acidic group, but W2 and Q may together form vinylidenethiazolidinedione or an equivalent heterocyclic ring; m and n represent an integer of 0 to 2, and q represents an integer of 0 to 3.

Disclosed are compounds which inhibit β-amyloid peptide release and/or its synthesis, and, accordingly, have utility in treating Alzheimer's disease. Also disclosed are pharmaceutical compositions comprising a compound which inhibits β-amyloid peptide release and/or its synthesis as well as methods for treating Alzheimer's disease both prophylactically and therapeutically with such pharmaceutical compositions.

Vitamin D compounds formula I wherein R represents hydrogen, or R represents (C1-C6)alkyl, phenyl, or (C7-C9)aralkyl, optionally substituted with one or more groups selected from (C1-C3)alkyl, F, phenyl; n is an integer having the value 0, 1, or 2; and X represents hydroxy or halogen.